US3442965A - Production of detergent alkylate and of olefines suitable for preparing such detergent alkylates - Google Patents

Production of detergent alkylate and of olefines suitable for preparing such detergent alkylates Download PDF

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US3442965A
US3442965A US554271A US3442965DA US3442965A US 3442965 A US3442965 A US 3442965A US 554271 A US554271 A US 554271A US 3442965D A US3442965D A US 3442965DA US 3442965 A US3442965 A US 3442965A
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hexene
dimerization
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Wilfred John Oldham
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    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
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Definitions

  • Detergent alkylates are prepared by alkylating an aromatic hydrocarbon with a branched chain olefin having from 10-16 carbon atoms.
  • the branched chain olefins are prepared by dimerizing straight chain 0 C, monoolefins with a catalyst comprising a synthetic petroleum cracking catalyst which may also contain an oxide of nickel, cobalt, manganese or chromium.
  • the present invention relates to the production of detergent alkylate which is biodegradable on sulphonation and is a continuation in part of my co-pending application Ser. No. 312,611 filed Sept. 30, 1963, of my copending application Ser. No. 280,449 filed May 14, 1963, and of my co-pending application Ser. No. 364,277 filed May 1, 1964, all of which are now abandoned.
  • detergent alkylate frac tions can be produced, which give-biologically degradable alkylbenzene sulphonates, but which do not consist predominantly of singly branched or straight chain alkylbenzenes, and which are made by dimerization of olefines over catalysts which give rapid rates of reaction and which are easier to use and handle than organometallic catalyst systems.
  • the process for the production of detergent alkylate comprises dimerizing a straight chain mono-olefine in the C to C carbon number range over a catalyst comprising a transition metal oxide or a synthetic petroleum cracking catalyst and condensing a fraction of the dimerization product in the C to C carbon number range with an "ice aromatic hydrocarbon in the presence of an alkylation catalyst.
  • the starting materials for the process of the present invention are straight chain mono-olefines having carbon numbers in the range C to C
  • the feedstock may be obtained in any suitable manner, for instance as a fraction of the products of thermally cracking a high molecular weight parafiinic hydrocarbon, preferably after purification to remove sulphur compounds, diolefines and acetylenic hydrocarbons.
  • Other suitable feedstocks are obtained by polymerization of lower olefines, especially ethylene, propylene or butene and isolation of a fraction from the polymer consisting of straight chain monoolefines having 5 to 8 carbon atoms.
  • the C to C straight chain olefine is prepared by dime'nizing propylene in the presence of a catalyst to form a product containing a substantial proportion of normal hexenes, and separating from the product a fraction consisting substantially of normal hexenes.
  • the propylene used as feedstock to this dimerization reaction may be pure propylene, or a fraction containing propylene, for example a C fraction from catalytic cracking, from a steam cracking process, or from thermal cracking operation. Since the catalysts for the propylene dimerization step are impaired by large amounts of acetylenes or propadiene, it is preferred that when these are present the C feedstock be pre-treated, for example by conventional selective hydrogenation processes, to remove most of these compounds prior to the propylene dimerization step. Sulphur compounds, water, and carbon monoxide also adversely alfect the performance of catalysts for propylene dimerization.
  • the C feedstock be free of higher boiling contaminants, particularly isobutene and branched hydrocarbons likely to form impurities in the dimerization step which would be difficult to separate from the normal hexenes produced. Propane functions merely as a diluent in this step, and its presence can therefore be tolerated.
  • the catalysts used in the dimerization of the propylene are those which will give dimerization products containing a substantial proportion of normal hexenes. It is preferred to use transition metal oxide catalysts since these give high yields of normal hexenes from propylene and produce only small amounts of branched chain isomers which are difficult to separate.
  • the preferred transition metal oxide catalyst is an oxide or oxides of nickel, cobalt, or chromium or mixtures thereof, and the use of nickel oxide catalysts is particularly preferred for this step.
  • the catalysts may be supported on carriers such as silica, silica gel or a silica/alumina cracking catalyst. A silica/alumina support is preferred.
  • the preparation of transition metal oxide catalysts of this type is described, for instance, by Holm et al. in Ind. Eng. Chem. 49, 250, 1957. These catalysts are activated by heating in air or oxygen at temperatures up to about 800 C., and periodic reactivation of the catalysts may be carried out similarly.
  • the dimerization of the propylene is suitably carried out at temperatures in the range of about 20 to 150 C. and preferably 40-80 C., desirably under suflicient pressure to maintain the reactants in the liquid phase.
  • An inert solvent, liquid under the reaction conditions, such as a low (C pa-rafiin may be used if desired.
  • the dimerization is preferably carried out with incomplete conversion of propylene for instance from 30- in order to minimise the formation of propylene polymers higher than the dimer but where other uses for higher polymers exist their formation may be no disadvantage and high propylene conversions can be used.
  • the separation from the propylene dimerization product of a fraction consisting substantially of normal hexenes may be carried out by known methods, using for instance molecular sieves, urea adduction or fractional distillation. Fractional distillation is the preferred method for carrying out this separation, which is critical in that no large amounts of branched chain hydrocarbons must be allowed to pass with the normal hexenes to the second dimerization step.
  • the main branched chain isomer formed in the dimerization of the propylene is 4-methyl-2- pentene, and the fractional distillation should be operated so as to separate this isomer substantially completely from the normal hexene fraction.
  • the propylene dimerization product is first distilled to separate unconverted propylene and the propane (if any is present), which may be recycled to the dimerization reactor; with feedstocks containing a high proportion of propane, withdrawal of a purge stream from the recycle propylene may be necessary to prevent build-up of propane in the system.
  • the dimerization product is then distilled to separate a distillate fraction consisting of methylpentenes, mainly 4-methyl- 2-pentene, and the residue is further distilled to recover a normal hexene distillate fraction, which is mainly a mixture of hexane-2 and -3 with some hexene-1 leaving as residue trimers and higher polymers of propylene.
  • the methylpentene fraction is a valuable by-product of the process, and may be converted, for instance, by double bond isomerization into a product which yields substantial amounts of isoprene on cracking.
  • Suitable C -C straight chain olefine fractions can also be made by dehydrogenation of C -C normal paraflins.
  • the dehydrogenation product may be fed to the dimerization reaction, and a fraction containing unreacted C to C normal parafiins recovered from the product and recycled to the dehydrogenation reactor.
  • the position of the double bond in the molecule is not critical in the C -C olefine feedstock, but the starting material should not contain an appreciable proportion of branched chain olefines.
  • the preferred transition metal oxide catalyst for the dimerization of the C to C olefines is an oxide or oxides of nickel, cobalt, maganese or chromium or mixtures thereof, and manganese oxide is a particularly suitable catalyst.
  • the catalysts are preferably deposited on supports such as silica, silica gel or a silica/alumina cracking catalyst.
  • One method for preparing transition metal oxide catalysts of this type is described, for instance, by Holm et al. in Ind. Eng. Chem. 49, 250, 1957. Periodic reactivation of the catalysts may be carried out by heating in an.
  • catalysts which may be used are the synthetic substances used in the cracking of petroleum. Typical examples of these are silica/alumina, silica/magnesia, silica/zirconia and silica/boria catalysts.
  • the preferred catalyst is silica/alumina, suitably containing between about 70% and about 90% by weight of silica, although the proportion of silica to alumina may vary within moderately wide limits.
  • the catalysts may be prepared in any suitable manner, and may be activated if desired, for instance by heating in air or inert gas such as nitrogen. Catalyst activation temperatures in the range from about 350 C. to about 650 C. are preferred.
  • the activity of 4 the catalyst tends to decline with long continued use, owing partly to the deposition of carbon on the catalyst surface, and may be restored in the conventional way, for instance by heating the catalyst in air to burn off the carbon.
  • these synthetic petroleum cracking catalysts can be operated for long periods without burning off the carbon. In this way treatment with an inert gas at high temperatures, preferably in excess of 150 C., will also restore lost activity at least partially without burning off the carbon.
  • the selectivity of the catalyst for the dimerization react-ion remains at a high level, and is not lowered by these treatments.
  • the dimerization step is suitably carried out at temperatures in the range of about 20 to 150 C. and preferably from 70 to 130 C., although with synthetic petroleum cracking catalysts good results may also be obtained at temperatures down to about 50 C. while it may be slightly less advantageous to work at temperatures above C.
  • the dimerization is preferably carried out under sufiicient pressure to maintain the reactants in the liquid phase. Suitable pressures are in the range 20 to 500 p.s.i.g., but higher and lower pressures can be used. Flow rates of olefines in the range 0.1 to 10 volumes of liquid olefine per volume of catalyst per hour are suitable.
  • the olefinic product from the second dimerization step is treated, preferably by fractional distillation, to separate a fraction containing the C -C normal olefine dimers, and within the C to C carbon atom range, but preferably extending over a range of not more than 5, and suitably not more than 4, carbon numbers, for use in the condensation reaction.
  • the dimerization product is first distilled to separate as distillate unpolyrnerized normal C -C olefines, which can be recycled.
  • the product is then fractionated, preferably under reduced pressure, to separate as distillate the required fraction containing the normal C -C olefine dimers.
  • the C -C olefine consists of n-hexenes this fraction consists primarily of dimers of normal hexenes and in a preferred embodiment the fractionation is carried out so as to separate substantially only dimers of normal hexenes as an overhead fraction.
  • the product from the second dimerization step contains little or no material other than C olefines.
  • the feed to the second dimerization step includes, in addition to the normal hexene distillate fraction prepared by propylene dimerization straight chain mono-olefines within the carbon number range C to C produced by other means as described above.
  • the products of the dimerization step are mostly olefines containing two or more branches in the chain, and only a small proportion of singly branched or normal olefines, such as n-dodecene.
  • the production of biologically degradable alkylbenzene sulphonates from these products is therefore surprising.
  • the recovered dimer fraction is condensed by known methods with an aromatic hydrocarbon in the presence of a suitable alkylation catalyst such as aluminium chloride or anhydrous hydrogen fluoride.
  • a suitable alkylation catalyst such as aluminium chloride or anhydrous hydrogen fluoride.
  • the aromatic hydrocarbon may be, for instance, benzene, toluene, xylenes 0r naphthalene; it is preferred to use benzene.
  • the preferred alkylation catalyst is hydrogen fluoride, which gives low proportions of unwanted low-boiling and high-boiling products.
  • the condensation is suitably carried out in the liquid phase at a temperature in the range of about -20 to +100 C.
  • the alkylation product after separation of the catalyst, is suitably fractionated to recover unreacted benzene for recycle, a small light alkylate fraction and a distillate detergent alkylate fraction, leaving a small residue of heavy alkylate.
  • a steam cracked C fraction containing approximately 95% of propylene, and small amounts of acetylenes and propadiene is treated with the required amount of hydrogen in a selective hydrogenation reactor 1 to reduce the amount of acetylenes and propadiene present, since these reduce the life of the dimerization catalyst used.
  • the treated propylene passes (after cooling and drying) to the still 2, where a small amount of polymeric material is left as residue and withdrawn by line 3, treated polymer-free propylene passing overhead to the first dimerization reactor 4.
  • This reactor is charged with nickel oxide on silica/ alumina catalyst, and maintained at a temperature in the range of 20-15 C., preferably 4080 C., under sufficient pressure to maintain liquid phase conditions.
  • the conversion in this step is kept relatively low to avoid forming high-boiling by-products, and the total products pass to the fractionator 10.
  • This fractionator removes normal hexenes as distillate, which are returned to the reactor 9.
  • the residue from fractionator 1 0, consisting of dimers of normal hexenes with a small amount of higher polymers is passed to fractionator 11.
  • This is operated under reduced pressure to produce a distillate olefine fraction consisting predominantly of dimers of normal hexenes and to discard a small residue of higher polymers.
  • the olefine distillate is passed to the HF alkylation system 12. To this is also fed fresh and recycle benzene by the line 13 and make up and recycle liquid anhydrous hydrogen fluoride by the line 14 respectively.
  • the alkylation is carried out under conventional conditions using a molar excess of benzene (suitably 5:1 to 20:1) over the olefine.
  • the total product from reactor 12 passes to the phase separator 15, where the HF layer is withdrawn and returned to the reactor 12.
  • a purge stream of hydrogen fluoride ' is withdrawn by the line 16; this is purified by distilling from polymeric material which otherwise builds up in the system, and can then be returned to the system.
  • the hydrocarbon layer from phase separator passes to the fractionator 17; here unreacted benzene is distilled 01f overhead together with the bulk of the HF remaining dissolved in the hydrocarbon and returned to the alkylator 12.
  • fractionator 17 The residue from fractionator 17 is passed to a wash system suitably using aqueous potassium hydroxide (not shown) to remove any remaining traces of hydrogen fluoride, and fractionated in column 18 (which is suit-ably operated under slightly reduced pressure) to take overhead any lower boiling material present and to correct the initial boiling point of the detergent alkylate product to the required level, and the residue passed to the fractionator 19.
  • a wash system suitably using aqueous potassium hydroxide (not shown) to remove any remaining traces of hydrogen fluoride
  • fractionated in column 18 which is suit-ably operated under slightly reduced pressure
  • This is operated under reduced pressure to give a detergent alkylate overhead distillate product which is withdrawn to storage, and a high boiling by-product (heavy alkylate) residue.
  • a hexene-l feedstock was passed in the liquid phase through a bed of this catalyst at a rate of 0.96 gms./gm. catalyst/hour, the temperature being -90 C. and the pressure 400 p.s.i.g.
  • the product was recovered and fractionated giving 11% of polymer, of which 80% was the required dimer.
  • the recovered monomer (89% of the total) contained about 20% hexene-l, the remainder being a mixture of hexene-Z and hexene-3.
  • the double bond isomerization of the monomer was rapid compared with the dimerization, so that the position of the double bond in the feedstock is not critical. No measurable skeletal isomerization of the feed occurred.
  • the dimer fraction so obtained was reacted with excess benzene (20 moles benzenezl mole dimer) with anhydrous fluoride as catalyst separated. Fractionation of the hydrocarbon product under reduced pressure gave a very small light alkylate fraction, and the main detergent alkylate product of boiling range between 25 8-294 C./ 760 mm. leaving a small residue of heavy alkylate.
  • the alkyl benzene so prepared was sulphonated with 22% oleum by a conventional method, and the sodium salt of the sulphonic acid isolated. This was then tested as follows. In the incubation test, solutions of 3-5 p.p.m. of sulphonate in river water were seeded with sewage efiluent (5 ml./1itre of sewage eflluent) and aerated at 20 C.
  • the Dobane/JN was a commercially available alkylate giving a sulphonate relatively susceptible to bio logical attack. It is clear from these results that the hexene dimer product was at least as susceptible to biological attack as the commercial product, and much more susceptible than the propylene tetramer.
  • Catalyst A was prepared using pelleted silica/alumina base heated to 550 C. in air. The cooled base was immersed in 18% aqueous formaldehyde solution for 5 minutes and excess solution filtered off, the solid rinsed with water, and immersed in saturated potassium permanganate solution for 10 minutes. The excess solution was filtered otf, and the catalyst washed with water to remove soluble inorganic materials. The solid catalyst was then dried at C. before charging the reaction, where it was heated in a stream of air at 550 C. for 5 hours and cooled in a stream of dry inert gas before starting the polymerization reaction.
  • Catalyst B was prepared by impregnating the same base with an aqueous solution of manganese nitrate, followed by the drying and heating treatment (to decompose the nitrate and activate the catalyst) used for catalyst A.
  • Catalyst for this run was that used in Run 4 after regenerating by heating in a stream of air at 500-550 0.
  • Example 3 The process described in Example 1 was repeated using a nickel oxide-silica-alumina (base containing 13% alumina) catalyst (C) prepared as in Example 1, or a nickel chloride catalyst (D) prepared as described in US. Patent 2,828,347.
  • alkylbenzene and alkylbenzene sulphonates were prepared from the olefine dimer and tested for biodegradability in the same way as in Example 1. Results are given in Table 3.
  • EXAMPLE 4 This illustrates the first dimerization step.
  • a nickel oxide on silica-alumina catalyst was prepared by the im- 8 pregnation method described by Holm et al. in Ind. Eng. Chem., 49, p. 250 (1957).
  • a propylene feed derived from catalytic cracking of petroleum fractions was used, hav ing the following composition:
  • This product can be fractionated to give a n-hexene fraction containing only very small amounts of branched chain hexenes.
  • EXAMPLE 5 This example illustrates the second dimerization step.
  • a manganese oxide/silica alumina catalyst was prepared as follows:
  • Pelleted silica alumina containing 13% alumina was ground to 18-30 mesh and heated to 550 C. in air to remove organic binding material.
  • the cooled granules were immersed in 18% formalin solution for 5 minutes and the excess formalin solution was filtered off.
  • the granules were briefly rinsed with water and then immersed in saturated potassium permanganate solution for 10 minutes.
  • the excess permanganate solution was filtered off and the granules washed thoroughly with water to remove all soluble inorganic materials.
  • the solid catalyst containing precipitated manganese dioxide was dried at C. before insertion in the polymerization reactor where it was heated in a stream of air at 550 C. for 5 hours before the polymerization reaction was started.
  • Fractions consisting substantially of n-hexene isomer mixtures were dimerised over the manganese dioxide/ silica alumina catalyst and over the nickel oxide/ silica alumina catalyst of Example 1.
  • the dimerization product was fractionally distilled to recover unpolymerised n-hexenes overhead, and the residue was fractionated under reduced pressure to recover a predominantly C product.
  • the distillate hexene dimer products were alkylated batchwise with benzene, using anhydrous hydrogen fluoride as catalyst, and the HF layer separated from the products.
  • the hydrocarbon layer was washed with aqueous potassium hydroxide to remove the remaining traces of hydrogen fluoride, dried, and fractionated to remove unreacted benzene.
  • the residue was then fractionated under reduced pressure to recover light alkylate, main detergent alkylate, and heavy alkylate products.
  • the detergent alkylate products were sulphonated in the conventional way, and the sodium salts of the sulphonic acid prepared. These sodium sulphonates were tested by incubating in dilute aqueous solution (ca. 10 ppm. of active agent) in river water seeded with sewage efiluent, and the active agent contents remaining after 23 days measured.
  • a sample of 4-methyl-pentene-1 was dimersized over nickel oxide/silica alumina catalyst and converted to alkylbenzenes as in Example 2. A better yield of the C alkylbenzene was obtained than from the Z-methylpentene-l dimer, although large amounts of lower alkylbenzene were formed with this material and the detergent alkylate yield was much lower than with the normal hexene dimers.
  • the alkylbenzene sulphonate was prepared and tested for biological oxidisability in the same way as in Example 2; the sulphonate was about as resistant to biological attack as the usual propylene tetramer benzene.
  • a dimer of 4-methylpentene-1 prepared using a Ziegler catalyst system also gave on conversion to alkylbenzene sulphonate a product which was relatively resistant to biological attack.
  • EXAMPLE 7 The tetramer (C fraction of a total polymerisation product prepared as illustrated in Example 1 was recovered by fractionation, this representing the propylene tetramer product obtained in a single-stage polymerization from propylene. This was then converted to an alkylbenzene sulphonate by the alkylation methods given in Example 2. This sulphonate proved to be extremely resistant to biological attack, showing that biologically oxidizable products cannot be made by a single-stage polymerization of propylene on the oxide catalysts.
  • EXAMPLE 8 A sample of Synclyst brand silica/alumina cracking catalyst containing about 13% by weight of alumina was sieved and the 18-30 mesh fraction calcined at 550 C. for 5 hours. The product was charged to a flow reactor and heated in a'stream of air at 540550 C. for 4 hours, and allowed to cool in nitrogen.
  • a mixed normal hexene feed containing 21% of hexene- 1 and 79% of hexene-Z and -3 was pumped over the catalyst at a rate of 1.3 gm./gm. catalyst/hour, a pressure of 400 p.s.i.g. and a temperature of 8090 C.
  • the catalyst was regenerated by heating in a stream of air at 530-560 C. for about 5 hours and again cooled in nitrogen. Reaction of the hexenes was then resumed under the same conditions until a further 60 parts of feed per part of catalyst had been processed.
  • the dimer product was alkylated to benzene using 20 moles of benzene and 20 moles of liquid hydrogen fluoride per mole of olefine, the reaction being carried out at 10-15 C.
  • the hydrocarbon layer was separated, washed with alkali, dried and fractionated to remove unconverted benzene, the residue (benzene free) was then fractionated under reduced pressure to give a distillate detergent alkylate product boiling between 260 and 315 C./ 760 mm. in a yield equivalent to 130 parts by weight per 100 parts of olefine fed to the alkylation.
  • 6.9 parts of residual heavy alkylate and 7.4 parts of light alkylate per 100 parts olefine were obtained.
  • the detergent alkylate product was sulphonated and the sodium sulphonate submitted to biological degradation tests, by incubating or aerating under standard conditions with sewage bacteria. Results for an existing commercial biodegradable material are included for comparison.
  • EXAMPLE 9 A sample of Synclyst brand silica/alumina cracking catalyst containing 13% by weight of alumina was sieved and the 18-30 mesh fraction heated in air at 550 C. for 7 hours. The product was charged to a tubular flow reactor, heated in a stream of air at 540 to 550 C. for 5 hours and allowed to cool in nitrogen.
  • a mixed normal hexene feed containing 24% hexene-1 and 76% of hexene-2 and hexene-3 was pumped over the catalyst at a temperature of 8090 C. and a pressure of 400 p.s.i.g.
  • the flow rate conditions and the conversion to total polymer over the course of the test were as follows:
  • EXAMPLE 10 This illustrates the effect of reaction temperature. Reactions were carried out using the catalyst of Example 9, but with different reaction temperatures and flow rates, the pressure still being 400 p.s.i.g. The results were as follows:
  • the 18-30 mesh fraction of a Synclyst silica/ alumina catalyst containing 13% of alumina was activated in a flow reactor by heating to 350 C. in a stream of nitrogen for hours.
  • the catalyst was then cooled and a normal hexene feed containing 96% of hexene-1 and 4% of hexene-2 and hexene-3 pumped over the catalyst at a flow rate of 1 -v./v./hr., a temperature of 80-90 C. and a pressure of 400 p.s.i.g.
  • the conversion to total polymer was 44.4% over the first sixteen hours of the run, which was then continued until the conversion fell to about 8%.
  • the C content of the bulked hexene-free polymer from the whole of this test was 85.3%.
  • the catalyst was then regenerated by treating with nitrogen for 5 hours at 350 C. After regeneration the polymerization was re sumed under the same conditions as before, giving a conversion to total polymer during the first 16 hours of 30.4%. The run was again continued until the conversion to total polymer was about 8%.
  • the bulked hexene-free polymer from the whole of this second part of the process contained 89.5% by weight of the C product, indicating that this regeneration method had no adverse effect or the efficiency of C formation from the normal hexenes.
  • EXAMPLE 12 This example illustrates the effect of activation temperature on the catalyst activity, and on the eificiency of formation of C olefines from normal hexenes.
  • a silica-alumina synthetic cracking catalyst containing 13% alumina was heated to various temperatures in air for 16 hours, and the resulting catalysts used in a dimerisation process with a normal hexene feed (consisting substantially of hexene-2), using a temperature of 63 C. and a flow rate of 1 volume/volume catalyst/hour. Each process was run for 6 hours and the total product analysed to determine the percentage of the hexenes converted to total polymer and the percentage of C olefines in the hexene-free polymer. The results were as follows:
  • EXAMPLE 13 This example shows the use of silica/ alumina catalysts containing 25% and 7% by weight of alumina. Each catalyst sample was activated in air for 16 hours at several temperatures, cooled and used for the dimerization of hexene-1 at a temperature of 63 C. and a flow rate of 1 volume/volume catalyst/hour under sufficient pressure to maintain liquid phase conditions. Each run was continued for 6 hours, and the conversion of hexene to total polymer and the percentage of C (hexene-dimer) in the total polymer measured gas chromatographically for the product from each 6-hour run.
  • EXAMPLE 14 A commercial silica/magnesla catalyst containing 30% of magnesium oxide was activated in air for 30 hours at 580 C., allowed to cool and used in the dimerization of hexene-1 at 63 C. using a flow rate of 1 volume/volume catalyst per hour. In a 6-hour run a conversion to total polymer of 8% was obtained, the total hexene-free polymer from the process containing 23% of C olefines.
  • a process for the production of a C -C olefin which has two or more branches which comprises dimerizing a straight chain C -C mono-olefin containing mainly internal olefins over a catalyst which comprises a synthetic petroleum cracking catalyst, recovering the C -C olefin, and recycling undimerized C -C straight chain mono-olefin containing mainly internal olefins to the dimerization reaction.
  • dimerization catalyst is an oxide of nickel, cobalt, manganese or chromium or mixtures thereof, deposited on silica/ alumina.
  • dimerization catalyst is periodically reactivated by heating in a medium selected from the group consisting of air and inert gases.
  • silica/ alumina contains from about 70-90% by weight of silica.
  • dimerization catalyst is activated by heating in a medium selected from the group consisting of air and inert gases to temperatures in the range 350 to 650 C.
  • dimerization catalyst is periodically reactivated by heating in a medium selected from the group consisting of air and inert gases.
  • the olefin is a C -C olefin having two or more branches produced by dimerizing a straight chain C -C monoolefin containing mainly internal olefins over a catalyst which comprises a synthetic petroleum cracking catalyst and recycling undimerized C -C straight chain monoolefins containing mainly internal olefins to the dimerization reaction.
  • the olefin is a C C olefin having two or more branches produced by dimerizing a straight chain C C mono-olefin containing mainly internal olefins over a catalyst which comprises an oxide of nickel, cobalt, manganese, chromium or mixtures thereof deposited on silica/ alumina, and recycling undimerized straight chain C -C mono-olefin containing mainly internal olefins to the dimerization reaction.
  • a process for the production of detergent alkylate which is biodegradable upon sulphonation which comprises alkylating an aromatic hydrocarbon in the presence of an alkylation catalyst with an olefin and recovering the detergent alkylate formed, the improvement wherein the olefin is a C -C fraction of olefins having two or more branches, which fraction contains a high proportion of C olefin, produced by dimerizing a straight chain C -C mono-olefin consisting essentially of mainly internal n-hexene in the presence of a catalyst comprising a synthetic petroleum cracking catalyst and recycling undimerized straight chain C -C mono-olefin containing mainly internal olefins to the dimerization reaction.

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Cited By (22)

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US4990718A (en) * 1989-04-03 1991-02-05 Mobil Oil Corporation Aromatic alkylation with alpha-olefin dimer
US6087529A (en) * 1996-03-12 2000-07-11 Exxon Chemical Patents Inc. Process for the stabilization of alkylbenzenesulphonates
US6274540B1 (en) 1997-07-21 2001-08-14 The Procter & Gamble Company Detergent compositions containing mixtures of crystallinity-disrupted surfactants
US6303556B1 (en) 1999-01-20 2001-10-16 The Procter & Gamble Company Hard surface cleaning compositions comprising modified alkybenzene sulfonates
US6342473B1 (en) 1999-01-20 2002-01-29 The Procter & Gamble Company Hard surface cleaning compositions comprising modified alkylbenzene sulfonates
US20020103096A1 (en) * 1997-07-21 2002-08-01 Kott Kevin Lee Alkylaryls
US6498134B1 (en) 1999-01-20 2002-12-24 The Procter & Gamble Company Dishwashing compositions containing alkylbenzenesulfonate surfactants
US6514926B1 (en) 1998-10-20 2003-02-04 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
US6525233B1 (en) 1997-08-08 2003-02-25 The Procter & Gamble Company Process for preparing a modified alkylaryl
US6566319B1 (en) 1997-07-21 2003-05-20 The Procter & Gamble Company Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof
US6583096B1 (en) 1998-10-20 2003-06-24 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
US6593285B1 (en) 1997-07-21 2003-07-15 The Procter & Gamble Company Alkylbenzenesulfonate surfactants
US6602840B1 (en) 1997-07-21 2003-08-05 The Procter & Gamble Company Processes for making alkylbenzenesulfonate surfactants and products thereof
WO2003029172A3 (de) * 2001-10-01 2003-10-30 Basf Ag Verfahren zur herstellung von alkylarylverbindungen und sulfonaten davon
US20040010161A1 (en) * 2000-08-11 2004-01-15 Heiko Maas Method for producing alkyl aryl sulphonates
US6774099B1 (en) 1999-01-20 2004-08-10 The Procter & Gamble Company Dishwashing detergent compositions containing mixtures or crystallinity-disrupted surfactants
WO2004072006A1 (en) * 2003-02-05 2004-08-26 Shell Internationale Research Maatschappij B.V. Method of preparing branched alkyl aromatic hydrocarbons using combined pprocess streams produced from hydrogenation, dehydrogenation, dimerization and isomerization of olefins
WO2004072005A1 (en) * 2003-02-05 2004-08-26 Shell Internationale Research Maatschappij B.V. Method of preparing branched alkyl aromatic hydrocarbons using a process stream from a dimerization unit
US20040176655A1 (en) * 2003-02-05 2004-09-09 Ayoub Paul Marie Methods of preparing branched alkyl aromatic hydrocarbons
US20050101808A1 (en) * 2003-10-15 2005-05-12 Ayoub Paul M. Methods of preparing branched aliphatic alcohols
WO2005037747A3 (en) * 2003-10-15 2005-06-16 Shell Oil Co Preparation of branched aliphatic alcohols using combined process streams from a hydrogenation unit, a dehydrogenation unit and an isomerization unit
US7202205B1 (en) 1999-09-01 2007-04-10 Daniel Stedman Connor Processes for making surfactants via adsorptive separation and products thereof

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US3193596A (en) * 1957-05-27 1965-07-06 Exxon Research Engineering Co Conversion of hydrocarbons
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US3109869A (en) * 1958-04-09 1963-11-05 Sinclair Research Inc Process for dimerizing olefins
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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4990718A (en) * 1989-04-03 1991-02-05 Mobil Oil Corporation Aromatic alkylation with alpha-olefin dimer
US6087529A (en) * 1996-03-12 2000-07-11 Exxon Chemical Patents Inc. Process for the stabilization of alkylbenzenesulphonates
US6908894B2 (en) 1997-07-21 2005-06-21 The Procter & Gamble Company Alkylaromatic hydrocarbon compositions
US6274540B1 (en) 1997-07-21 2001-08-14 The Procter & Gamble Company Detergent compositions containing mixtures of crystallinity-disrupted surfactants
US6602840B1 (en) 1997-07-21 2003-08-05 The Procter & Gamble Company Processes for making alkylbenzenesulfonate surfactants and products thereof
US20020103096A1 (en) * 1997-07-21 2002-08-01 Kott Kevin Lee Alkylaryls
US6593285B1 (en) 1997-07-21 2003-07-15 The Procter & Gamble Company Alkylbenzenesulfonate surfactants
US6566319B1 (en) 1997-07-21 2003-05-20 The Procter & Gamble Company Cleaning products comprising improved alkylarylsulfonate surfactants prepared via vinylidene olefins and processes for preparation thereof
US6525233B1 (en) 1997-08-08 2003-02-25 The Procter & Gamble Company Process for preparing a modified alkylaryl
US6514926B1 (en) 1998-10-20 2003-02-04 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
US6583096B1 (en) 1998-10-20 2003-06-24 The Procter & Gamble Company Laundry detergents comprising modified alkylbenzene sulfonates
US6498134B1 (en) 1999-01-20 2002-12-24 The Procter & Gamble Company Dishwashing compositions containing alkylbenzenesulfonate surfactants
US6342473B1 (en) 1999-01-20 2002-01-29 The Procter & Gamble Company Hard surface cleaning compositions comprising modified alkylbenzene sulfonates
US6303556B1 (en) 1999-01-20 2001-10-16 The Procter & Gamble Company Hard surface cleaning compositions comprising modified alkybenzene sulfonates
US6774099B1 (en) 1999-01-20 2004-08-10 The Procter & Gamble Company Dishwashing detergent compositions containing mixtures or crystallinity-disrupted surfactants
US7202205B1 (en) 1999-09-01 2007-04-10 Daniel Stedman Connor Processes for making surfactants via adsorptive separation and products thereof
US20040010161A1 (en) * 2000-08-11 2004-01-15 Heiko Maas Method for producing alkyl aryl sulphonates
US7060852B2 (en) * 2000-08-11 2006-06-13 Basf Aktiengesellschaft Method for producing alkyl aryl sulphonates
US20060167308A1 (en) * 2000-08-11 2006-07-27 Basf Aktiengesellschaft Process for the preparation of alkylarylsulfonates
US20040254411A1 (en) * 2001-10-01 2004-12-16 Ulrich Steinbrenner Method for producing alkylaryl compounds and sulfonates thereof
WO2003029172A3 (de) * 2001-10-01 2003-10-30 Basf Ag Verfahren zur herstellung von alkylarylverbindungen und sulfonaten davon
US7566799B2 (en) 2001-10-01 2009-07-28 Basf Aktiengesellschaft Process for the preparation of alkylaryl compounds and sulfonates thereof
WO2004072005A1 (en) * 2003-02-05 2004-08-26 Shell Internationale Research Maatschappij B.V. Method of preparing branched alkyl aromatic hydrocarbons using a process stream from a dimerization unit
US20040176655A1 (en) * 2003-02-05 2004-09-09 Ayoub Paul Marie Methods of preparing branched alkyl aromatic hydrocarbons
WO2004072006A1 (en) * 2003-02-05 2004-08-26 Shell Internationale Research Maatschappij B.V. Method of preparing branched alkyl aromatic hydrocarbons using combined pprocess streams produced from hydrogenation, dehydrogenation, dimerization and isomerization of olefins
US20050101808A1 (en) * 2003-10-15 2005-05-12 Ayoub Paul M. Methods of preparing branched aliphatic alcohols
WO2005037747A3 (en) * 2003-10-15 2005-06-16 Shell Oil Co Preparation of branched aliphatic alcohols using combined process streams from a hydrogenation unit, a dehydrogenation unit and an isomerization unit
US7335802B2 (en) 2003-10-15 2008-02-26 Shell Oil Company Methods of preparing branched aliphatic alcohols

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